CN111961354A - Ceramic pigment and application thereof - Google Patents
Ceramic pigment and application thereof Download PDFInfo
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- CN111961354A CN111961354A CN202010846524.8A CN202010846524A CN111961354A CN 111961354 A CN111961354 A CN 111961354A CN 202010846524 A CN202010846524 A CN 202010846524A CN 111961354 A CN111961354 A CN 111961354A
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- glaze
- ceramic pigment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/0009—Pigments for ceramics
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention provides a ceramic pigment and application thereof, and a preparation method of the ceramic pigment comprises the following steps: (1) calcining the red mud in an oxidizing atmosphere at the highest temperature of 1100-1350 ℃ to obtain a calcined product, wherein the red mud comprises the following chemical components in parts by weight: 3-8 parts of Na2O, 0-3 parts of MgO, and 10-16 parts of Al2O33-8 parts of SiO20 to 2 parts of P2O51-4 parts of CaO and 6-12 parts of TiO2And 48-56 parts of Fe2O3(ii) a (2) And pulverizing the calcined product to obtain the ceramic pigment. The invention provides a ceramic pigment and application thereof, the ceramic pigment takes red mud as a raw material, realizes solid waste utilization, saves cost, simultaneously limits chemical composition and mineral composition of the red mud, and further limits calcined ceramic pigmentThe temperature ensures that the color change range of the ceramic pigment is wide, and the application range of the ceramic pigment is improved.
Description
Technical Field
The invention relates to the field of ceramics, in particular to a ceramic pigment and application thereof.
Background
The red mud is waste residue discharged in the alumina production industry, and generally 1.0-2.0 tons of red mud is additionally generated when 1 ton of alumina is produced on average. China, the fourth alumina producing country in the world, discharges red mud as high as millions of tons every year. The red mud has complex chemical components and mainly contains CaO and Al2O3、SiO2、Fe2O3、Na2O、TiO2And the like. A large amount of red mud cannot be fully and effectively utilized, and only depends on a large-area yard, thereby occupying a large amount of land and causing serious pollution to the environment. Therefore, how to fully and effectively recycle the red mud in large quantities to develop novel materials of industrial solid wastes and reduce the harm to the environment becomes an urgent task at present.
The ceramic pigment is a ceramic product decorative material with large industrial production demand, and according to preliminary statistics, the pigment for ceramic glaze used in China is more than 8 ten thousand tons every year, and the pigment for blank is more than 16 ten thousand tons. The stability and the color tone diversity of the ceramic pigment are the targets of the production of the ceramic pigment. In particular, with the emphasis on recycling of industrial solid waste resources, research and development of high-quality ceramic coloring materials from inexpensive industrial solid waste as a raw material to reduce production costs are important in research and development of ceramic coloring materials.
Patent CN201210068708.1 discloses a method for preparing brown ceramic pigment from red mud, which is prepared from red mud and chemical raw materials such as chromium oxide, iron oxide red, aluminum hydroxide or aluminum oxide, zinc oxide, etc. However, the method also needs to add chemical raw materials such as chromium oxide, iron oxide red, aluminum hydroxide or aluminum oxide, zinc oxide and the like, and the preparation cost is high.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a ceramic pigment and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the ceramic pigment comprises the following steps:
(1) calcining red mud in oxidizing atmosphereThe highest temperature is 1100-1350 ℃, and a calcined product is obtained, wherein the red mud comprises the following chemical components in parts by weight: 3-8 parts of Na2O, 0-3 parts of MgO, and 10-16 parts of Al2O33-8 parts of SiO20 to 2 parts of P2O51-4 parts of CaO and 6-12 parts of TiO2And 48-56 parts of Fe2O3The mineral composition of the red mud comprises the following components in parts by weight: 10-25 parts of hematite, 20-35 parts of limonite, 8-18 parts of goethite, 2-5 parts of gibbsite, 1-4 parts of boehmite, 3-6 parts of diaspore, 4-6 parts of quartz, 3-6 parts of anatase, 4-7 parts of rutile, 1-3 parts of cancrinite and 0-2 parts of hydrocalumite;
(2) and pulverizing the calcined product to obtain the ceramic pigment.
The red mud is industrial solid waste discharged when aluminum oxide is extracted in the aluminum production industry, and has larger deviation of chemical components and mineral compositions due to different production methods and technical levels. The main minerals of red mud are aragonite and calcite, followed by opal, gibbsite, goethite, and the least abundant are titanium ore (anatase and rutile) and siderite. The optimization of the chemical components of the red mud raw material is realized by limiting the chemical components and the calcination temperature of the red mud raw material, so that the color change range of the prepared ceramic pigment is wide. The color of the ceramic pigment, which varies with the maximum firing temperature and chemical composition, varies from orange to brown. The effect of the color change is realized mainly because the ceramic pigment preferably selects the chemical components of the red mud, and hematite (alpha-Fe) is in the red mud mineral composition2O3) In octahedral coordination of (3), Fe3+Occupying the main absorption band (within the visible light band range of 300-700 nm) of the coloring material, and at the calcining temperature of 1100 ℃, the ceramic coloring material has three visible light absorption bands: fe in hematite3+The 6A1 → 4E (4D) coordination transition of (A-H) induces an absorption band around 360 nm; fe3+The 6A1 → 4E transition of (1) induces an absorption band around 430 nm; fe in hematite2+→Fe3+The valence charge transfer of (2) induces an absorption band around 650 nm. While absorption bands around 360nm, 430nm and 650nm all result in red-orange stainingTherefore, the ceramic coloring material is orange in color at the calcination temperature of 1100 ℃. When the calcining temperature is increased to over 1200 ℃ (1350 ℃), the hematite (alpha-Fe) in the red mud mineral composition2O3) With anatase and rutile (TiO)2) Reacting under high-temperature calcination to generate pseudobrookite (Fe)2TiO5) And the crystal phase initiates cation vacancy, so that the ceramic pigment is brown at the calcining temperature of 1200-1350 ℃. The ceramic pigment has wide color change range, improves the application range of the ceramic pigment, realizes the utilization of solid waste and saves the cost.
Preferably, the red mud comprises the following chemical components in parts by weight: 7-8 parts of Na2O, 2.5-3 parts of MgO, and 14.5-16 parts of Al2O33-7 parts of SiO21.5 to 2 parts of P2O51-3.5 parts of CaO and 6-12 parts of TiO2And 52-56 parts of Fe2O3。
Preferably, in the step (2), the method for pulverizing the calcined product comprises the steps of: and mixing the calcined product with water, ball-milling to obtain red mud slurry, drying, screening and collecting 50-65 mu m powder to obtain the ceramic pigment.
Preferably, the ball milling speed is 250-350 rmp, the ball milling time is 1-3 hours, and the weight ratio of the calcined product, the grinding balls and the water is (0.8-1.2): (3.5-4.5): 0.8-1.2.
Preferably, in the step (1), the calcination is carried out at the highest temperature for 3 to 5 hours.
Preferably, in the step (1), the calcination is carried out by raising the temperature to the highest temperature by a program, wherein the temperature is raised to 100 ℃ at a temperature raising rate of 2-6 ℃/min and then is kept for 20-40 minutes, and the temperature is raised to the highest temperature at a temperature raising rate of 2-6 ℃/min and then is kept for 3-5 hours, and then the calcination is cooled.
The invention provides a ceramic glaze which comprises any one of the ceramic pigments, wherein the ceramic pigment accounts for 2-6% of the weight of the ceramic glaze.
Preferably, the ceramic glaze is ceramicA transparent glazing comprising a ceramic pigment according to any one of claims 1 to 5 and a ceramic raw material comprising the following components in parts by weight: 40-55 parts of SiO230-45 parts of Al2O35-12 parts of ZrO2And 0 to 5 parts of P2O5。
The ceramic glaze uses the red mud as a raw material, and has beautiful color and low cost.
Preferably, the ceramic glaze is a ceramic white glaze comprising the ceramic pigment according to any one of claims 1 to 5 and a ceramic raw material, wherein the ceramic raw material comprises the following components in parts by weight: 55-65 parts of SiO25 to 15 parts of Al2O38-15 parts of CaO, 5-15 parts of ZnO and 2-8 parts of K2O and 1-5 parts of B2O3。
The ceramic glaze uses the red mud as a raw material, and has beautiful color and low cost.
Preferably, the ceramic glaze is a ceramic matt glaze, which comprises the ceramic pigment according to any one of claims 1 to 5 and a ceramic raw material, wherein the ceramic raw material comprises the following components in parts by weight: 50-62 parts of SiO215 to 27 parts of Al2O38-15 parts of CaO and 2-8 parts of K2O and 1-5 parts of MgO.
The ceramic glaze uses the red mud as a raw material, and has beautiful color and low cost.
The invention has the beneficial effects that: the ceramic pigment provided by the invention takes the red mud as a raw material, so that solid waste utilization is realized, the cost is saved, the chemical composition and the mineral composition of the red mud are limited, the calcining temperature is further limited, the color change range of the ceramic pigment is wide, and the application range of the ceramic pigment is widened.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
The invention provides a ceramic pigment, and a preparation method of the ceramic pigment comprises the following steps:
(1) calcining the red mud in an oxidizing atmosphere at the highest temperature of 1100-1350 ℃ to obtain a calcined product, wherein the red mud comprises the following chemical components in parts by weight: 3-8 parts of Na2O, 0-3 parts of MgO, and 10-16 parts of Al2O33-8 parts of SiO20 to 2 parts of P2O51-4 parts of CaO and 6-12 parts of TiO2And 48-56 parts of Fe2O3The mineral composition of the red mud comprises the following components in parts by weight: 10-25 parts of hematite, 20-35 parts of limonite, 8-18 parts of goethite, 2-5 parts of gibbsite, 1-4 parts of boehmite, 3-6 parts of diaspore, 4-6 parts of quartz, 3-6 parts of anatase, 4-7 parts of rutile, 1-3 parts of cancrinite and 0-2 parts of hydrocalumite;
(2) and pulverizing the calcined product to obtain the ceramic pigment.
The invention provides a ceramic glaze which comprises the ceramic pigment, wherein the ceramic pigment accounts for 2-6% of the weight of the ceramic glaze.
Example 1
The preparation method of the ceramic pigment provided by the embodiment of the invention comprises the following steps:
(1) calcining the red mud in an oxidizing atmosphere, wherein the highest temperature of the calcination is 1100 ℃, the calcination is carried out by raising the temperature to the highest temperature through a program, the temperature is raised to 100 ℃ at a temperature raising rate of 3 ℃/min and then is preserved for 35 minutes, the temperature is raised to 1100 ℃ at a temperature raising rate of 2 ℃/min and then is preserved for 3.5 hours, and the red mud is cooled to obtain a calcined product, wherein the red mud comprises the following chemical components in parts by weight: 7 parts of Na2O, 2.5 parts of MgO, 14.5 parts of Al2O37 parts of SiO21.5 parts of P2O53.5 parts of CaO, 12 parts of TiO2And 52 parts of Fe2O3(ii) a The mineral weight composition of the red mud is 25 parts of hematite, 35 parts of limonite, 15 parts of goethite, 2 parts of gibbsite, 2 parts of boehmite, 3 parts of diaspore, 5 parts of quartz, 5 parts of anatase, 6 parts of rutile, 1 part of cancrinite and 1 part of hydrocalumite
(2) And pulverizing the calcined product to obtain the ceramic pigment, wherein the method for pulverizing the calcined product comprises the following steps: mixing and ball-milling the calcined product and water to obtain red mud slurry, drying the red mud slurry in a ventilation oven at 85 ℃, screening and collecting 50-65 mu m powder to obtain a ceramic pigment, wherein the ball-milling speed is 350rmp, the ball-milling time is 2.5 hours, and the weight ratio of the calcined product to the grinding balls to the water is 1:4: 1.
Example 2
As a ceramic color material in the present example, the only difference between this example and example 1 is that the maximum temperature of calcination was 1350 ℃.
Example 3
The ceramic glaze provided by the embodiment of the invention comprises the ceramic pigment provided by the embodiment 1, wherein the ceramic pigment provided by the embodiment 1 accounts for 5% of the weight of the ceramic glaze, the ceramic glaze is a ceramic transparent glaze, and the ceramic white glaze further comprises the following chemical components in parts by weight: 55 parts of SiO235 parts of Al2O38 parts of ZrO2And 2 parts of P2O5。
The preparation method of the ceramic glaze comprises the following steps: the ceramic pigment of example 1 and the rest of the raw materials were wet mixed according to the weight ratio, ball milled for 35 minutes, dried at 80 ℃ and sieved with a 65 μm sieve, and after sieving, calcined at 1100 ℃ for 30 minutes.
Example 4
The ceramic glaze provided by the embodiment of the invention comprises the ceramic pigment provided by the embodiment 1, wherein the ceramic pigment provided by the embodiment 1 accounts for 5% of the weight of the ceramic glaze, the ceramic glaze is a ceramic white glaze, and the ceramic white glaze further comprises the following chemical components in parts by weight: 60 parts of SiO210 parts of Al2O312 parts of CaO, 10 parts of ZnO and 6 parts of K2O and 2 parts of B2O3。
The preparation method of the ceramic glaze comprises the following steps: the ceramic pigment of example 1 and the rest of the raw materials were wet mixed according to the weight ratio, ball milled for 35 minutes, dried at 80 ℃ and sieved with a 65 μm sieve, and after sieving, calcined at 1100 ℃ for 30 minutes.
Example 5
The ceramic glaze provided by the embodiment of the invention comprises the ceramic pigment provided by the embodiment 1, wherein the ceramic pigment provided by the embodiment 1 accounts for 5% of the weight of the ceramic glaze, the ceramic glaze is a ceramic matt glaze, and the ceramic matt glaze further comprises the following chemical components in parts by weight: 58 parts of SiO218 parts of Al2O312 parts of CaO, 7 parts of K2O and 5 parts of MgO.
The preparation method of the ceramic glaze comprises the following steps: the ceramic pigment of example 1 and the rest of the raw materials were wet mixed according to the weight ratio, ball milled for 35 minutes, dried at 80 ℃ and sieved with a 65 μm sieve, and after sieving, calcined at 1100 ℃ for 30 minutes.
Effect example 1
The color performance of the ceramics obtained in examples 1 and 2 is shown in Table 1.
TABLE 1 ceramic pigment Properties
The red mud glazes obtained in examples 3, 4 and 5 were compared in their properties as follows. Different glaze and color effects are realized by optimizing ceramic glaze types (transparent glaze, white glaze and matt glaze).
TABLE 2 ceramic glaze Properties
Tables 1 and 2 show that the ceramic coloring material of the present invention has a wide color change range and an improved application range.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The ceramic pigment is characterized in that the preparation method of the ceramic pigment comprises the following steps:
(1) calcining the red mud in an oxidizing atmosphere at the highest temperature of 1100-1350 ℃ to obtain a calcined product, wherein the red mud comprises the following chemical components in parts by weight: 3-8 parts of Na2O, 0-3 parts of MgO, and 10-16 parts of Al2O33-8 parts of SiO20 to 2 parts of P2O51-4 parts of CaO and 6-12 parts of TiO2And 48-56 parts of Fe2O3The mineral composition of the red mud comprises the following components in parts by weight: 10-25 parts of hematite, 20-35 parts of limonite, 8-18 parts of goethite, 2-5 parts of gibbsite, 1-4 parts of boehmite, 3-6 parts of diaspore, 4-6 parts of quartz, 3-6 parts of anatase, 4-7 parts of rutile, 1-3 parts of cancrinite and 0-2 parts of hydrocalumite;
(2) and pulverizing the calcined product to obtain the ceramic pigment.
2. The ceramic pigment according to claim 1, wherein the red mud comprises the following chemical components in parts by weight: 7-8 parts of Na2O, 2.5-3 parts of MgO, and 14.5-16 parts of Al2O33-7 parts of SiO21.5 to 2 parts of P2O51-3.5 parts of CaO and 6-12 parts of TiO2And 52-56 parts of Fe2O3。
3. The ceramic pigment according to claim 1, wherein in the step (2), the method for pulverizing the calcined product comprises the steps of: and mixing the calcined product with water, ball-milling to obtain red mud slurry, drying, screening and collecting 50-65 mu m powder to obtain the ceramic pigment.
4. The ceramic pigment of claim 3, wherein the ball milling speed is 250 to 350rmp, the ball milling time is 1 to 3 hours, and the weight ratio of the calcined product, the grinding balls and the water is (0.8 to 1.2): (3.5 to 4.5): 0.8 to 1.2.
5. The ceramic pigment according to claim 1, wherein in the step (1), the calcination is performed by raising the temperature to a maximum temperature by a program, wherein the temperature is raised to 100 ℃ at a temperature raising rate of 2-6 ℃/min and then is maintained for 20-40 minutes, and the temperature is raised to the maximum temperature at a temperature raising rate of 2-6 ℃/min and then is maintained for 3-5 hours, and then the ceramic pigment is cooled.
6. A ceramic glaze, characterized in that it comprises a ceramic pigment according to any one of claims 1 to 5, the ceramic pigment according to any one of claims 1 to 5 being present in an amount of 2% to 6% by weight of said ceramic glaze.
7. The ceramic glaze according to claim 6, wherein the ceramic glaze is a ceramic transparent glaze, the ceramic transparent glaze comprises the ceramic pigment according to any one of claims 1 to 5 and a ceramic raw material, and the ceramic raw material comprises the following components in parts by weight: 40-55 parts of SiO230-45 parts of Al2O35-12 parts of ZrO2And 0 to 5 parts of P2O5。
8. The ceramic glaze according to claim 6, wherein the ceramic glaze is a ceramic white glaze, the ceramic white glaze comprises the ceramic pigment according to any one of claims 1 to 5 and a ceramic raw material, and the ceramic raw material comprises the following components in parts by weight: 55-65 parts of SiO25 to 15 parts of Al2O38-15 parts of CaO, 5-15 parts of ZnO and 2-8 parts of K2O and 1-5 parts of B2O3。
9. The method of claim 6The ceramic glaze of (1), wherein the ceramic glaze is a ceramic matt glaze, the ceramic matt glaze comprises the ceramic pigment according to any one of claims 1 to 5 and a ceramic raw material, and the ceramic raw material comprises the following components in parts by weight: 50-62 parts of SiO215 to 27 parts of Al2O38-15 parts of CaO and 2-8 parts of K2O and 1-5 parts of MgO.
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| CN202010846524.8A CN111961354A (en) | 2020-08-21 | 2020-08-21 | Ceramic pigment and application thereof |
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| CN202010846524.8A CN111961354A (en) | 2020-08-21 | 2020-08-21 | Ceramic pigment and application thereof |
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Cited By (2)
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| CN114380502A (en) * | 2022-01-27 | 2022-04-22 | 佛山市百善孝先无机化学原料有限公司 | Dry ceramic particles with pearl effect and preparation method and application method thereof |
| CN115286360A (en) * | 2022-07-12 | 2022-11-04 | 德化恒瀚艺品有限公司 | Production process of medium-temperature laterite ceramic |
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| CN114380502A (en) * | 2022-01-27 | 2022-04-22 | 佛山市百善孝先无机化学原料有限公司 | Dry ceramic particles with pearl effect and preparation method and application method thereof |
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| CN115286360A (en) * | 2022-07-12 | 2022-11-04 | 德化恒瀚艺品有限公司 | Production process of medium-temperature laterite ceramic |
| CN115286360B (en) * | 2022-07-12 | 2023-09-08 | 德化恒瀚艺品有限公司 | Production process of medium-temperature laterite ceramic |
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Application publication date: 20201120 |